中文摘要：

运用M06-2X和ωB97XD方法分别在6-311＋＋G（2d, p）和TZVP基组水平上,对脯氨酸（Pro）的15种构象与Cu、Cu＋和Cu2＋形成的多种配合物的几何结构、能量学特征、振动光谱和电子结构等进行计算研究.四种水平得到20种[Pro-Cu]、16种[Pro-Cu]＋和16种[Pro-Cu]2＋稳定结构.[Pro-Cu]和[Pro-Cu]＋体系中出现12种Pro构象,而[Pro-Cu]2＋体系中出现11种Pro构象,三种体系中最稳定的结构都不是由能量最低的Pro构象生成的.在结构CI3、CI4、CII7和CII8中, Pro的羧基氢转移到亚氨基氮形成两性离子与Cu双配位结合.[Pro-Cu]0/1＋/2＋体系四种水平计算相对能差范围逐渐增加,结合能分别在-60.0--5.0 kJ·mol-1、-340.0--170.0 kJ·mol-1和-1100.0--860.0 kJ·mol-1范围,配位体系中Pro的变形能逐渐增加. N-H和O-H键伸缩振动频率普遍发生红移,配位体系中部分电荷从Pro转移到Cu上,在[Pro-Cu]2＋体系中单配位结构中电荷转移最多,约为单位负电荷.

英文摘要：

The geometric and electronic structures, energetics, and vibrational frequencies of different coordinate systems formed between 15 conformers of proline （Pro） and Cu, Cu＋, and Cu2＋were investigated in detail, using the M06-2X andωB97XD methods with 6-311＋＋G（2d, p） and TZVP basis sets. A total of 20, 16, and 16 stable [Pro-Cu]0/1＋/2＋complexes were obtained at four levels. These structures demonstrated that 12 conformers of Pro exist in the [Pro-Cu] and [Pro-Cu]＋systems, while 11 conformers are present in the [Pro-Cu]2＋complexes. The most stable complexes are evidently not formed by the lowest energy conformer of Pro with Cu, Cu＋, and Cu2＋. In the CI3, CI4, CII7, and CII8 complexes, the carboxyl group hydrogen of Pro was found to transfer to the imino nitrogen to form a zwitterion. Both the relative energy difference and the deformation energy of Pro gradual y increase along with the charge number of the Cu. The binding energies of the [Pro-Cu]0/1＋/2＋systems were determined to be in the ranges of-60.0 to-5.0,-340.0 to-170.0, and-1100.0 to-860.0 kJ·mol-1, respectively. The stretching vibrational frequencies of the N-H and O-H bonds in Pro all exhibit a general red shift on complexation. Additional y, each system shows charge transfer from the Pro to the Cu, even in the case of [Pro-Cu]2＋, some complexes that have more than one negative charge.